Diphenylamines N-monosubstituted in the 4&#39;-position and the use thereof in dye compositions for keratinic fibers

ABSTRACT

Diphenylamine which is N-monosubstituted in the 4&#39;-position carries at least one acylamino group at the 2- or 6-position. The diphenylamine is usefully employed in a composition for dyeing keratinic fibers.

This is a continuation of application Ser. No. 884,817, filed Mar. 9, 1978, now abandoned which in turn is a continuation of application Ser. No. 743,497, filed Nov. 19, 1976, now abandoned, which is a division of Ser. No. 551,627, filed Feb. 21, 1975, now U.S. Pat. No. 4,008,043.

The present invention relates to diphenylamines or N-alkyl leuco indoanilines monosubstituted in the 4' position, to their preparation and to their use for dyeing keratinic fibers, and in particular living human hair.

BACKGROUND OF THE INVENTION

A currently utilized technique for dyeing keratinic fibers, and especially living human hair, comprises applying to the hair, in the presence of an oxidizing agent added at the moment of use (generally hydrogen peroxide), a dye composition comprising a mixture in an appropriate cosmetic support, of compounds belonging to one or the other of the two following classes.

The first class of compounds, generally called "oxidation bases" is principally constituted by paraphenylenediamines or paraaminophenols which, on oxidation, produce para benzoquinonediimines or parabenzoquinonemonoimines.

The second class of compounds, generally called "couplers" include, especially, metaaminophenols, metaacetylaminophenols, metadiamines and metadiphenols. These compounds which when reacted with benzoquinone mono- or di-imines produce dyes which, depending upon their structure, are called indophenols, indoanilines or indamines.

These dyes, which provide a range of shades of exceptional richness, importantly are characterized by the luminosity and the richness in glints of dyeings or colorations they impart to the fibers dyed therewith.

However, when a complex dye composition is employed, i.e. a composition which includes several bases and several couplers, it is very difficult to foresee in the final shade the contribution of each possible couple of oxidation base and coupler. In other words, on the one hand, it is very difficult at the outset to predict with any exactitude the final shade that will be attained and, on the other hand, for a given dye composition it is not often easy to be assured of a perfectly reproducible result. These difficulties are increased by the fact that different secondary reactions can modify the final shade, such secondary reactions including, for instance, formation of Bandrowsky base type compounds starting with oxidation bases; recondensation of a molecule of an oxidation base on certain indophenols or on certain indoanilines or indamines; and formation of quinones and the like.

Heretofore it has also been proposed to use in the dyeing of hair some indoanilines which are well defined compounds and which impart to the hair essentially perfectly reproducible shades.

However, some inconvenience has been experienced in the use of these compounds since they possess only a slight affinity for keratinic fibers under conventional conditions for dyeing hair.

SUMMARY OF THE INVENTION

The present invention relates to leuco derivatives of indoanilines which are colorless compounds and which, when applied in an aqueous solution to fibers to be dyed, are oxidized at the interior of the keratinic fibers so as to give the corresponding indoanilines. These resulting indoanilines are the colored compounds which are directly responsible for the dyeing of the fibers. The colorations thus obtained exhibit stability and intensity of coloration qualities which are greater than those of dyeings effected by the direct application of indoanilines, because of the enhanced solubility and better keratinic fiber penetration characteristics of the compounds of the present invention.

The oxidation of leuco derivatives of the present invention to indoanilines can be effected by the oxygen in air or by the use of an oxidizing agent incorporated into the dye composition at the moment of use. Representative oxidizing agents include hydrogen peroxide, urea peroxide and ammonium persulfate.

While the use of the leuco derivatives of indoaniline for dyeing hair has already been proposed, the present invention enlarges the family of such leuco derivatives. Thus the leuco derivatives of indoanilines or diphenylamines of the present invention have the formula ##STR1## wherein R₁ and R₄ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, amino, N-lower alkyl amino, N-lower hydroxyalkyl amino, N-lower carbamylalkyl amino, acylamino, ureido and carbalkoxyamino,

R₂ and R₃ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, acylamino and ureido,

R₅ and R₆ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy and can occupy any two free positions on the phenylene ring with the proviso however that when they are both other than hydrogen, at least one of R₅ and R₆ occupies a position meta relative to the --NHR₇ group, i.e. it occupies position 2' or 6'; and

R₇ represents a member selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower amino alkyl, lower acylaminoalkyl, lower mesylamino alkyl, lower carbamylalkyl, lower sulfoalkyl, lower piperidinoalkyl, lower morpholino alkyl, lower monoalkyl lower aminoalkyl and lower dialkyl lower aminoalkyl.

The above lower alkyl group contains from 1 to 6 and preferably 1 to 4 carbon atoms and the above acyl group contains 2-7 carbon atoms.

The present invention also relates to diphenylamines of formula (I) in the form of their salts, such as, for instance, the hydrochlorides, hydrobromides, sulfates and phosphates thereof.

The diphenylamines of formula (I) are the leuco derivatives of indoanilines of the formula (II) ##STR2## wherein R₁ to R₇ have the meanings given above, and can be obtained by the reduction of these indoanilines, preferably by catalytic hydrogenation of the same in the presence of a palladium on carbon catalyst. Alternatively, these indoanilines can be reduced using an alkaline hydrosulfite, preferably sodium or ammonium hydrosulfite, or using an alkaline sulfide, preferably ammonium sulfide.

The diphenylamines of the present invention are usefully employed to dye keratinic fibers and, in particular, living human hair. These diphenylamines, when applied to hair in an aqueous or hydroalcoholic solution, at a concentration ranging between 0.002 to 3 weight percent thereof and preferably between 0.1 to 1 weight percent, provide after oxidation either with air or by another oxidizing agent such as hydrogen peroxide, urea peroxide or ammonium persulfate a range of shades which are very rich in the area of pinks to violets, blues and greens. Additionally, the diphenylamines of the present invention provide some very luminous grays and beiges which are rich in glints. The dyeings thus obtained are characterized by richness in glints and their pearly or metallic aspect.

The present invention also relates to a dye composition for keratinic fibers and in particular living human hair, comprising an aqueous or hydroalcoholic solution, and preferably hydroethanolic or hydroisopropanolic solution, containing at least one compound of formula (I).

The dye composition can also include a salt of the diphenylamines of formula (I) and in particular the hydrochloride, hydrobromide, sulfate or phosphate thereof.

The dye composition according to the present invention can include as the active dyeing agent only the compounds of formula (I). However, they can also include other known leuco derivatives of inodanilines, indamines or indophenols, or even oxidation dyes such as ortho- or para-phenylenediamines or ortho- or para-aminophenols, as well as couplers such as metadiamines, metadiphenols, metaaminophenols, metaacetylaminophenols or even direct dyes such as nitrobenzene dyes, azo dyes or anthraquinone dyes, indoanilines, indamines and/or indophenols.

The compositions according to the present invention are generally provided in the form of an aqueous or hydroalcoholic solution containing one or more compounds of formula (I), in admixture or not with other dyes. They can, however, also include thickening agents and be provided in the form of a cream or gel.

Representative thickening agents that can be incorporated into the dye composition of the present invention include cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose or acrylic polymers such as the sodium salt of polyacrylic acid or carboxyvinyl polymers.

The dye composition can contain as solvents, water, lower alkanols for example ethanol or isopropanol, polyalcohols such as glycols, for example, ethylene glycol, propylene glycol, butyl glycol, diethyleneglycol and the monomethyl ether of diethylene glycol.

The dye composition according to the present invention can also include other components generally employed in cosmetics, such as sequesterants, including ethylene diamine tetra acetic acid and salts thereof; wetting agents including oxyethylenated alkyl phenols, oxyethylenated fatty acids, oxyethylenated fatty alcohols, sulfates and sulfonates of fatty alcohols optionally oxyethylenated; dispersing agents such as the diethanolamides of fatty acids of coprah; swelling agents; penetrating agents; emollients; polymers and/or perfumes. The composition of the present invention can also be packaged in aerosol containers together with an aerosol propellant.

Representative aerosol propellants usefully employed in compositions according to the present invention include nitrogen, nitrous oxide, volatile hydrocarbons such as butane, isobutane or propane, or preferably fluorinated hydrocarbons (sold under the name of Freon by Dupont) such as dischlorodifluoromethane, 1,1-difluoromethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane and 1-chloro-1,1-difluoromethane. Mixtures of two or more hydrocarbons or fluorinated hydrocarbons can also be used.

The pH of the compositions of the present invention can vary widely and generally it ranges between about 5.5 to 12 and preferably between about 6 and 11.

The pH of the composition can be adjusted with the aid of an alkalizing agent such as, for example, ammonia, mono-, di- or tri-ethanolamine, di- or tri-sodium phosphate, sodium carbonate or potassium carbonate, or with the aid of an acidifying agent such as, for example, acetic acid, lactic acid, phosphoric acid or citric acid.

The dyeing of keratinic fibers and, in particular, living human hair, with the use of the dye compositions of the present invention, is carried out in a conventional manner by applying the said composition to the fibers to be dyed, permitting said composition to remain in contact with the fibers for a period of time ranging from about 5 to 30 minutes rinsing and optionally washing the fibers and then drying the fibers. Prior to applying the said composition to the fibers, there can be added to said composition an oxidizing agent such as 25-100 percent by volume of hydrogen peroxide, generally 6% (20 volumes), or 0.1 to 15% by weight of an oxidizing agent such as urea peroxide or ammonium persulfate.

The compositions according to the present invention, when present in the form of a hydroalcoholic solution, can also include a cosmetic resin, so as to provide a colored hair setting lotion which can be applied to wet or moist hair before setting.

Representative cosmetic resins that can be used in the hair setting lotion composition of the present invention include such film-forming polymers of polyvinylpyrrolidone; copolymers of polyvinylpyrrolidone and vinyl acetate; copolymers of vinyl acetate and an unsaturated carboxylic acid such as crotonic acid; copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and an acrylic or methacrylic ester; copolymers resulting from the copolymerization of vinyl acetate and a vinyl alkyl ether; copolymers resulting from the copolymerization of vinyl acetate crotonic acid and a vinyl ester of a long carbon chain acid or even of an allyl or methallyl ester of a long carbon chain acid; copolymers resulting from the copolymerization of an ester derived from an unsaturated alcohol and a short carbon chain acid, of an unsaturated short carbon chain acid and of at least one ester derived from a short carbon chain saturated alcohol and an unsaturated acid; and copolymers resulting from the copolymerization of at least one unsaturated ester and at least one unsaturated acid.

Representative preferred cosmetic resins include polyvinylpyrrolidone having a molecular weight ranging between about 10,000 to 360,000; copolymers of 10% crotonic acid and 90% vinyl acetate having a molecular weight ranging between about 10,000 to 70,000; copolymers of vinylpyrrolidone and vinyl acetate having a molecular weight ranging between about 30,000 to 200,000 wherein the ratio of VP to VA ranges between 30:70 to 70:30; copolymers of maleic anhydride and methylvinyl ether in a 1 to 1 molar ratio, having a specific viscosity, measured at 25° C. and at a concentration of 1 g in 100 ml of methyl ethyl ketone ranging between about 0.1 and 3.5; the monoethyl, monoisopropyl and monobutyl esters of said maleic anhydride methyl vinyl ether copolymers; copolymers of maleic anhydride and vinylbutyl ether in a 1 to 1 molar ratio; terpolymers of methyl methacrylate (15-25%) stearyl methacrylate (18-28%) and dimethylaminoethyl methacrylate (52-62%); and terpolymers of vinyl acetate (75-85%), allyl stearate (10-20%) and allyloxy-acetic acid (3-10%); the viscosity of which, measured at the boiling point of ether and at a concentration of 5% in dimethylformamide, ranges between about 4.4 and 5 centipoise.

These cosmetic film-forming resins are used generally in an amount between about 1-3 percent by weight of the total hair setting lotion composition.

The alcohols generally employed in the production of the hair setting lotion compositions of the present invention are low molecular weight alcohols, preferably ethanol or isopropanol. These alcohols are used in an amount of about 20 to 70 weight percent of the total composition.

The hair setting lotion composition of the present invention can be utilized in a conventional manner by applying the same to wet or moist hair, previously washed and rinsed, followed by rolling the hair upon curlers and drying the hair.

The preparation of benzoquinoneimines used as initial reactants for the preparation of the diphenylamines takes place by condensing a compound of formula (III), below, in which Z is NO or NH₂ and R₅, R₆ and R₇ have the meanings given above, or a salt thereof, on a phenolic compound of formula IV, below, wherein R₁, R₂, R₃ and R₄ have the meanings given above, or a salt thereof. ##STR3##

When Z represents --NH₂, the condensation is carried out in an aqueous, hydroalcoholic or hydroacetonic medium at an alkaline pH generally greater than 8, in the presence of an oxidizing agent, for example, ammonium persulfate, potassium ferricyanide and hydrogen peroxide, and at a temperature generally ranging between about 0° to 25° C. The alkaline pH is obtained by means of ammonia or an alkaline carbonate such as sodium carbonate.

When Z represents --NO, the condensation is carried out generally at a temperature of about 50° C., in a hydroethanolic medium which is neutral or has been made alkaline by the addition thereto of a dilute sodium hydroxide solution.

The preparation of the diphenylamines of the present invention can advantageously be effected in accordance with the following operation.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

To a solution of sodium hydrosulfite in 1N sodium hydroxide to which has been added ethanol and which is maintained at a temperature ranging between about 10° to 40° C., there is added, little by little and with agitation, the benzoquinoneimine in the form of a suspension or a partial solution or a complete solution, in ethanol. The agitation of the resulting mixture is continued and when the reaction is terminated, the reaction medium is filtered to remove any insolubles if such are formed. The reaction medium, cooled to 0° C., is neutralized by adding solid carbon dioxide or acetic acid in an amount sufficient to precipitate the desired leuco derivative. The precipitate is recovered by filtering the reaction medium and is washed with water eventually saturated with carbonic gas. If necessary, the leuco derivative can be recrystallized in a mixture of dimethyl formamide and water and then dried under a vacuum.

The diphenylamines in which R₁ or R₄ represents an amino group can be prepared starting with benzoquinoneimine having an acetyl-amino group in the indicated position. On deacetylation the benzoquinoneimine corresponding to the diphenylamine is formed, which benzoquinoneimine is then reduced as indicated above.

The following procedures which illustrate the preparation of 3-methoxy-4-hydroxy-6-amino-4'-N-methylamino diphenylamine, indicated below as Example 49, are representative of the method to prepare diphenylamines of the present invention, wherein R₁ or R₄ represent an amino group.

In a first stage, carried out at 0° C., as described above, the dihyddrochloride of N-methyl paraphenylene diamine is condensed on 2-methoxy-5-acetylaminophenol, in a hydroacetonic medium and in the presence of ammonium persulfate. The molar ratio of the said phenolic compound to aniline compound is 1:1 and the molar ratio of the said oxidizing agent to the phenolic compound is 2:1. There is obtained N-[(4'-methylamino)phenyl]-2-methoxy-5-acetylamino benzoquinoneimine having a melting point of 207° C.

    ______________________________________                                                         C %    H %      N %                                            ______________________________________                                         Calculated for C.sub.16 H.sub.17 N.sub.3 O.sub.3                                                 64.21    5.69     14.04                                      Found             63.97    5.91     14.15                                      ______________________________________                                    

In a second stage, 0.005 mole of N-[(4'-methylamino)phenyl]-2-methoxy-5-acetylamino benzoquinoneimine in 50 cc of a normal sodium hydroxide solution to which has been added 20 cc of ethanol is agitated at ambient temperature. The said benzoquinoneimine is completely de-acetylated and there is recovered by filtration 1.1 g of N-[(4'-methylamino)phenyl]-2-methoxy-5-amino benzoquinoneimine which, after recrystallization in a mixture of dimethylformamide and water is dried under a vacuum, has the characteristics indicated in Example 49 of Table A below.

In a third stage, the N-[4'-methylamino)phenyl]-2-methoxy-5-amino benzoquinoneimine is reduced under the conditions appearing in Example 49 of Table II, below, to form 3-methoxy-4-hydroxy-6-amino-4'-N-methylamino diphenylamine having the characteristics given in Example 49 of Table I, below.

The characteristics of the benzoquinoneimine initial reactants given in Table A, infra, wherein Column I indicates the number of the compound; Column II, its chemical name; Column III, the empirical formula of said compound; Column IV, the melting point of the compound and Column V the elemental analysis of the compound with percentages of carbon, hydrogen, nitrogen and optionally chlorine and sulfur. For the indicated percentages, the first number indicated represent the value calculated for the empirical formula given whereas the second and third numbers represent the value found by analysis.

In Table B are listed the operating conditions for preparing the benzoquinoneimines and the various columns of Table B indicate the number of the compound prepared, the names of the initial reactants (anilines and phenols), the mole ratio of said phenol to said aniline, the nature of the reaction medium, the nature of the oxidizing agent, the mole ratio of oxidizing agent to phenolic compound and the temperature of the reaction.

                                      TABLE A                                      __________________________________________________________________________     I   II                    III IV         V                                                               MP             Analyses                              Ex No                                                                              BENZOQUINONEIMINE     (°C.)                                                                       Empirical Formula                                                                         C  H  N  Cl S                         __________________________________________________________________________     1   N-[(4'-β-hydroxyethylamino-3'-methyl)-                                                          242 C.sub.18 H.sub.21 N.sub.3 O.sub.3                                                         66.03                                                                             6.47                                                                              12.84                               phenyl]-2-methyl 5-acetylamino       65.85                                                                             6.65                                                                              12.93                                                                    65.87                                                                             6.44                                                                              13.06                           2   N-[(4'-β-acetylaminoethylamino-3'-metho-                                                        183 C.sub.19 H.sub.24 N.sub.4 O.sub.3                                                         64.02                                                                             6.79                                                                              15.72                               xy)-phenyl]-2,6-dimethyl-5-amino     63.87                                                                             6.58                                                                              15.51                                                                    63.74                                                                             6.70                                                                              15.20                           3   N-[(4'-β-mesylamino ethylamino-3'-chloro)                                                       244 C.sub.18 H.sub.21 N.sub.4 O.sub.4 S                                                       50.88                                                                             4.98                                                                              13.18 7.54                          phenyl]-2-methyl-5-acetylamino       50.71                                                                             5.20                                                                              13.36 7.26                                                               50.77                                                                             5.20                                                                              13.42 7.38                      4   N-[(4'-ethylamino-2'methyl)phenyl]-                                                                  212 C.sub.16 H.sub.18 N.sub.4 O.sub.2                                                         64.41                                                                             6.08                                                                              18.78                               3-ureido                             64.29                                                                             6.25                                                                              18.47                                                                    64.58                                                                             6.09                                                                              18.62                           5   N-[(4'-β-mesylaminoethylamino-3'-methyl)                                                        148 C.sub.20 H.sub.26 N.sub.4 O.sub.4 S                                                       57.40                                                                             6.26                                                                              13.39 7.64                          phenyl]-2,6-dimethyl-5-acetylamino   57.52                                                                             6.24                                                                              13.53 7.66                                                               57.23                                                                             6.27                                                                              13.45 7.44                      6   N-[(4'-ethylamino-3'-methyl)phenyl]-2,6-                                                             147 C.sub.17 H.sub.21 N.sub.3 O                                                               72.05                                                                             7.47                                                                              14.83                               dimethyl-3-amino                     71.78                                                                             7.42                                                                              15.04                                                                    71.67                                                                             7.53                                                                              14.65                           7   N-[(4'-ethylamino)phenyl]2-methyl-5-                                                                 225 C.sub.17 H.sub.20 N.sub.4 O.sub.2                                                         65.36                                                                             6.45                                                                              17.94                               carbamylmethylamino                  65.06                                                                             6.59                                                                              18.16                                                                    65.08                                                                             6.64                                                                              18.04                           8   N-[(4'-ethylamino)phenyl]2-methyl-5-                                                                 100 C.sub.17 H.sub.19 N.sub.3 O.sub.2                                                         68.66                                                                             6.44                                                                              14.13                               acetylamino                          68.12                                                                             6.44                                                                              13.98                                                                    68.41                                                                             6.66                                                                              13.94                           9   N-[(4'-methylamino)phenyl] 2,6-dimethyl-                                                             158 C.sub.17 H.sub.19 N.sub.3 O.sub.2                                                         68.66                                                                             6.44                                                                              14.13                               3-acetylamino                        68.29                                                                             6.57                                                                              14.25                                                                    68.32                                                                             6.58                                                                              14.34                           10  N-[(4'-methylamino-3'-methoxy)phenyl]                                                                156 C.sub.16 H.sub.18 N.sub.2 O.sub.2                                                         71.09                                                                             6.71                                                                              10.36                               2,6-dimethyl                         70.86                                                                             6.83                                                                              10.42                                                                    70.79                                                                             6.76                                                                              10.49                           11  N-[(4'-β-hydroxyethylamino-3'-chloro)                                                           144 C.sub.16 H.sub. 15 N.sub.3 O.sub.3 Cl.sub.2                                               52.19                                                                             4.10                                                                              11.41                                                                             19.26                            phenyl]-3-chloro-6-acetylamino       52.05                                                                             4.42                                                                              11.52                                                                             19.16                                                                 51.93                                                                             4.38                                                                              19.23                           12  N-[(4'-ethylamino-3'-chloro)phenyl]                                                                  144 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl                                                      61.53                                                                             5.46                                                                              12.66                                                                             19.68                            2-methyl-5-acetylamino               61.57                                                                             5.61                                                                              12.53                                                                             10.79                                                                 61.28                                                                             5.51                                                                              12.86                                                                             10.65                        13  N-[(4'-β-hydroxyethylamino-3'-methoxy)                                                          110 C.sub.19 H.sub.23 O.sub.4 N.sub.3,H.sub.2                                                 60.79                                                                             6.71                                                                              11.19                               phenyl]-2,6-dimethyl-5-acetylamino   60.53                                                                             6.58                                                                              11.31                                                                    60.45                                                                             6.61                                                                              11.36                           14  N-[(4'-butylamino-3'-chloro)phenyl]                                                                  124 C.sub.18 H.sub.20 N.sub.3 O.sub.2 Cl                                                      62.52                                                                             5.80                                                                              12.15                                                                             10.25                            3-acetylamino                        62.35                                                                             6.03                                                                              12.21                                                                             10.40                                                                 62.29                                                                             6.04                                                                              12.09                                                                             10.17                        15  N-[(4'-β-acetylaminoethylamino-3'-                                                              156 C.sub.17 H.sub.18 N.sub.3 O.sub.3 Cl                                                      58.70                                                                             5.18                                                                              12.08                               chloro)phenyl]-3-methoxy             58.41                                                                             4.97                                                                              12.20                                                                    58.56                                                                             5.04                                                                              12.17                           16  N-[(4'-ethylamino-3'-methyl)phenyl]                                                                  211 C.sub.18 H.sub.21 N.sub.3 O.sub.3                                                         66.06                                                                             6.42                                                                              12.84                               2-methoxy-5-acetylamino              65.93                                                                             6.33                                                                              13.04                           17  N-[(4'-methylamino-3'-methoxy)phenyl]-2-                                                             179 C.sub.18 H.sub.21 N.sub.3 O.sub.4                                                         62.96                                                                             6.16                                                                              12.24                               methyl-5-carbethoxyamino             63.02                                                                             6.28                                                                              12.06                           18  N-[(4'-methylamino-2'-chloro)phenyl]-2-                                                              190 C.sub.16 H.sub.18 N.sub.3 O.sub.2 Cl                                                      60.09                                                                             5.67                                                                              13.14                                                                             11.11                            methyl-5-β-hydroxyethylamino    60.15                                                                             5.86                                                                              13.31                                                                             11.19                        19  N-[(4'-methylamino)phenyl]-2-methyl-                                                                 162 C.sub.14 H.sub.15 N.sub.3 O                                                               69.69                                                                             6.27                                                                              17.42                               5-amino                              68.52                                                                             6.33                                                                              17.62                                                                    68.57                                                                             6.39                                                                              17.55                           20  N-[(4'-methylamino-2-40 -chloro) phenyl]                                                             235 C.sub.17 H.sub.18 Cl N.sub.3 O.sub.2                                                      61.53                                                                             5.47                                                                              12.66                                                                             10.68                            2,6-dimethyl-5-acetylamino           61.26                                                                             5.56                                                                              12.90                                                                             10.47                        21  N-[(4'-methylamino-2'-methoxy)phenyl]                                                                249 C.sub.18 H.sub.21 N.sub.3 O.sub.3                                                         66.03                                                                             6.47                                                                              12.84                               2,6-dimethyl-5-acetylamino           65.84                                                                             6.52                                                                              12.79                           22  N-[(4'-methylamino-2'-chloro) phenyl]                                                                234 C.sub.16 H.sub.16 N.sub.3 O.sub.2 Cl                                                      60.47                                                                             5.07                                                                              13.22                               2-methyl-5-acetylamino               60.42                                                                             5.29                                                                              13.18                           23  N-[(4'-methylamino)phenyl]2,6-dimethyl                                                               132 C.sub.15 H.sub.16 N.sub.2 O                                                               74.97                                                                             6.71                                                                              11.66                                                         MW = 240 (a)                                                                              74.68                                                                             6.91                                                                              11.44                                                         MW = 239 (b)                                     24  N-[(4'-methylamino-3'-methyl)phenyl]2,6-                                                             138 C.sub.16 H.sub.18 N.sub.2 O                                                               75.56                                                                             7.13                                                                              11.02                               dimethyl                             75.69                                                                             7.12                                                                              11.11                           25  N-[(4'-methylamino-3'-chloro)phenyl]2-                                                               127 C.sub.15 H.sub.15 Cl N.sub.2 O                                                            65.58                                                                             5.50                                                                              10.19                                                                             12.90                            2,6-dimethyl                         65.41                                                                             5.60                                                                              10.24                                                                             12.90                        26  N-[(4'-methylamino-3'-methyl)phenyl]2-                                                               166 C.sub.15 H.sub.17 N.sub.3 O                                                               70.56                                                                             6.71                                                                              16.46                               methyl-5-amino                       70.33                                                                             6.72                                                                              16.34                           27  N-[(4'-β-hydroxyethylamino-3'-methoxy)                                                          150 C.sub.16 H.sub.19 N.sub.3 O.sub.3                                                         63.77                                                                             6.36                                                                              13.95                               phenyl]-2-methyl-5-amino             63.81                                                                             6.53                                                                              14.02                                                                    64.02                                                                             6.65                                                                              14.19                           28  N-[(4'-methylamino-3'-methyl)phenyl]                                                                 152 C.sub.16 H.sub.19 N.sub.3 O                                                               71.34                                                                             7.11                                                                              15.60                               2,6-dimethyl-5-amino                 71.20                                                                             7.01                                                                              15.73                           29  N-[(4'-methylamino)phenyl]2,6-dimethyl-                                                              166 C.sub.15 H.sub.17 N.sub.3 O                                                               70.56                                                                             6.71                                                                              16.46                               3-amino                              70.75                                                                             6.67                                                                              16.49                                                         MW = 255 (a)                                                                              70.41                                                                             6.68                                                                              16.52                                                         MW = 251 (b)                                     30  N-[(4'-methylamino-3'-chloro)phenyl]                                                                 198 C.sub.15 H.sub.14 N.sub.3 O.sub.2 Cl                                                      59.31                                                                             4.61                                                                              13.84                               3-acetylamino                        59.21                                                                             4.81                                                                              13.93                           31  N-[(4'-methylamino)phenyl]2-methyl-5-                                                                161 C.sub.16 H.sub.17 N.sub.3 O.sub.2                                                         67.82                                                                             6.05                                                                              14.83                               acetylamino                          67.72                                                                             6.18                                                                              14.92                           32  N-[(4'-methylamino-3'-methyl)phenyl]                                                                 210 C.sub.17 H.sub.19 N.sub.3 O.sub.2                                                         68.66                                                                             6.44                                                                              14.13                               2-methyl-5-acetylamino                                                                               210 C.sub.17 H.sub.19 N.sub.3 O.sub.2                                                         68.66                                                                             6.44                                                                              14.13                               2-methyl-5-acetylamino               68.64                                                                             6.49                                                                              14.28                           33  N-[(4'-ethylamino-3'-methyl)phenyl]                                                                  185 C.sub.17 H.sub.21 N.sub.3 O.sub.2                                                         69.45                                                                             6.75                                                                              13.50                               2-methyl-5-acetylamino               69.20                                                                             7.00                                                                              13.74                           34  N-(4'-β-hydroxyethylamino-3'-chloro)                                                            178 C.sub.16 H.sub.16 N.sub.3 O.sub.3 Cl                                                      57.57                                                                             4.79                                                                              12.59                                                                             10.64                            phenyl]phenyl]3-acetylamino          57.39                                                                             4.79                                                                              12.71                                                                             10.48                        35  N-[(4'-β-hydroxyethylamino-3'-chloro)                                                           176 C.sub.17 H.sub.18 N.sub.3 O.sub.3 Cl                                                      58.70                                                                             5.18                                                                              12.08                                                                             10.21                            phenyl]2-methyl-5-acetylamino        58.83                                                                             5.19                                                                              12.17                                                                             10.36                        36  N-[(4'-methylamino-3'-chloro)phenyl]                                                                 166 C.sub.17 H.sub.18 Cl N.sub.3 O.sub.2                                                      61.53                                                                             5.47                                                                              12.66                                                                             10.68                            2,6-dimethyl-5-acetylamino           61.61                                                                             5.62                                                                              12.51                                                                             10.53                        37  N-[(4'-methylamino-3'-methyl)phenyl]                                                                 160 C.sub.18 H.sub.21 N.sub.3 O.sub.2                                                         69.43                                                                             6.80                                                                              13.50                               2,6-dimethyl-3-acetylamino           69.36                                                                             6.73                                                                              13.28                           38  N-[(4'-methylamino-3'-chloro)phenyl]                                                                 206 C.sub.16 H.sub.16 Cl N.sub.3 O.sub.2                                                      60.45                                                                             5.07                                                                              13.22                               2-methyl-5-acetylamino               60.35                                                                             5.23                                                                              13.31                           39  N-[(4'-methylamino-3'-chloro)phenyl]                                                                 218 C.sub.16 H.sub.17 N.sub.4 O.sub.2 Cl                                                      57.74                                                                             5.11                                                                              16.84                           40  N-[(4'-methylamino-3'-chloro)phenyl]                                                                 258 C.sub.14 H.sub.13 N.sub.4 O.sub.2 Cl                                                      55.17                                                                             4.27                                                                              18.39                                                                             11.66                            3-ureido                             55.14                                                                             4.56                                                                              18.64                                                                             11.57                        41  N-[(4'-β-hydroxyethylamino-3'-chloro)                                                           195 C.sub.17 H.sub.19 N.sub.4 O.sub.3 Cl                                                      56.30                                                                             5.24                                                                              15.42                                                                             9.79                             phenyl] 2,6-dimethyl-3-ureido        56.41                                                                             5.34                                                                              15.33                                                                             9.81                         42  N-[(4'-β-hydroxyethylamino-3'-chloro)                                                           280 C.sub.15 H.sub.15 N.sub.4 O.sub.3 Cl                                                      53.81                                                                             4.48                                                                              16.74                                                                             10.61                            phenyl] 3-ureido                     53.86                                                                             4.71                                                                              16.62                                                                             10.36                        43  N-[(4'-methylamino-3'-chloro)phenyl]                                                                 228 C.sub.15 H.sub.15 N.sub.4 O.sub.2 Cl                                                      56.51                                                                             4.71                                                                              17.58                                                                             11.14                            2-methyl-5-ureido                    56.61                                                                             4.90                                                                              17.63                                                                             10.93                        44  N-[(4'-β-hydroxyethylamino-3'-chloro)                                                           240 C.sub.16 H.sub.17 N.sub.4 O.sub.3 Cl                                                      55.09                                                                             4.88                                                                              16.07                                                                             10.18                            phenyl] 2-methyl-5-ureido            54.84                                                                             4.97                                                                              16.03                                                                             10.18                                                                 54.83                                                                             4.91                                                                              16.00                                                                             10.30                        45  N-[(4'-methylamino-3'-chloro)phenyl]                                                                 120 C.sub.16 H.sub.17 N.sub.4 O.sub.2 Cl                                           · H.sub.2 O                                                                      54.78                                                                             5.46                                                                              16.26                                                                             10.,11                           2-methyl-5-carbamylmethylamino                                                                       212 (c)        54.67                                                                             5.16                                                                              16.53                                                                             10.13                        46  N-[(4'-methylamino)phenyl] 2-methyl                                                                  228 C.sub.16 H.sub.18 N.sub.4 O.sub.2                                                               17.71                               5-carbamylmethylamino · H.sub.2 O                                                                             17.40                                                            MW = 298 (a)                                                                   MW = 304 (b)                                     47  N-[(4'-methylamino-3'-chloro)phenyl]                                                                 120 C.sub.15 H.sub.15 ClN.sub.2 O                                                             65.57                                                                             5.50                                                                              10.20                                                                             12.90                            2,5-dimethyl                         65.56                                                                             5.60                                                                              10.19                                                                             12.91                        48  monohydrate of N-[(4'-methylamino-                                                                   258 C.sub.15 H.sub.13 N.sub.3 O.sub.2 Cl.sub.2                                                      11.79                                                                             19.94                            2'-chloro) phenyl] 2-chloro-5-acetylamino                                                                H.sub.2 O        11.94                                                                             19.58                                                                       11.88                                                                             19.57                        49  monohydrate of N-[(4'-methylamino]                                                                   117 C.sub.14 H.sub.15 N.sub.3 O.sub.2                                              · H.sub.2 O                                                                      61.08                                                                             6.18                                                                              15.27                               2-methoxy-5-amino                       60.94                                                                             6.25                                                                              15.36                        __________________________________________________________________________      (a) molecular weight calculated                                                (b) molecular weight determined by potentiometric dosing in acetic acid        with perchloric acid                                                           (c) double melting point                                                 

                                      TABLE B                                      __________________________________________________________________________                                                           Molar                                                        Molar             Ratio of                                                     Ratio of          oxidizing                Example                 PHENOLIC    phenol/                                                                             Reaction                                                                              Oxidizing                                                                            agent                                                                               Temp.               No   ANILINE (Substituted)                                                                             COMPOUND    aniline                                                                             Medium Agent phenol                                                                              (°C.)        __________________________________________________________________________     1    2-methyl-4-amino-N-(β-hydroxyethyl)                                                          2-methyl-5-acetylamino                                                                      1:1 acetone-water                                                                         ammonium                                                                              2:1 0                        aniline sulfate    phenol                  persulfate                     2    2-methoxy-4-amino-N-(β-acetylamino-                                                          2,6-dimethyl-5-amino                                                                       1:1  water  ammonium                                                                             1:1  0                        ethyl) aniline sulfate                                                                            phenol hydrochloride    persulfate                     3    2-chloro-4-amino-N-(β-mesylamino-                                                            2-methyl-5-acetylamino                                                                     1:1  acetone-water                                                                         ammonium                                                                             2:1  0                        ethyl) aniline sulfate                                                                            phenol                  persulfate                     4    3-methyl-4-amino-N-ethylaniline                                                                   3-ureido phenol                                                                            1:1  acetone-water                                                                         ammonium                                                                             1:1  0                        dihydrochloride                            persulfate                     5    2-methyl-4-amino-N-(β-mesylamino-                                                            2,6-dimethyl-5-ace-                                                                        1:1  acetone-water                                                                         ammonium                                                                             1:1  0                        ethyl) aniline sulfate                                                                            tylamino phenol         persulfate                     6    2-methyl-4-nitroso-N-ethylaniline                                                                 2,6-dimethyl-3-amino                                                                       1:1  ethanol-water     40                                          phenol hydrochloride                                   7    4-nitroso-N-ethylaniline                                                                          2-methyl-5-carbamyl-                                        hydrochloride      methylamino phenolthanol-water     50                  8    N-ethyl paraphenylene diamine                                                                     2-methyl-5-acetylamino                                                                     1:1  acetone-water                                                                         ammonium                                                                             1:1  0                        dihydrochloride    phenol                  persulfate                     9    N-methyl paraphenylenediamine                                                                     2,6-dimethyl-3-ace-                                                                        1:1  acetone-water                                                                         ammonium                                                                             1:1  0                        dihydrochloride    tylamino phenol         persulfate                     10   2-methoxy-4-amino-N-methylaniline                                                                 2,6-dimethyl phenol                                                                        1:1  acetone-water                                                                         ammonium                                                                             2:1  0                        sulfate                                    persulfate                     11   2-chloro-4-amino-N-(β-hydroxyethyl)                                                          3-chloro-6-acetyl-                                                                         1:1  water-acetone                                                                         ammonium                                                                             1:1  0                        aniline sulfate    amino phenol            persulfate                     12   2-chloro-4-amino-N-ethylaniline                                                                   2-methyl-5-acetyl-                                                                         1:1  acetone-water                                                                         ammonium                                                                             1:1  0                        sulfate            amino phenol            persulfate                     13   2-methoxy-4-amino-N-(β-hydroxyethyl)                                                         2,6-dimethyl-5-ace-                                                                        1:1  water-acetone                                                                         ammonium                                                                             1.1:1                                                                               0                        aniline sulfate    tylamino phenol         persulfate                     14   2-chloro-4-amino N-butylaniline                                                                   3-acetylamino phenol                                                                       1:1  acetone-water                                                                         ammonium                                                                             1:1  0                        sulfate                                    persulfate                     15   2-chloro-4-amino N-(β-acetylamino-                                                           3-methoxyphenol                                                                            1:1  acetone-water                                                                         ammonium                                                                             2:1  0                        ethyl) aniline sulfate                     persulfate                     16   2-methyl-4-amino N-ethylaniline                                                                   2-methoxy-5-acetyl-                                                                        1:1  acetone-water                                                                         ammonium                                                                             2:1  0                        sulfate            amino phenol            persulfate                     17   2-methoxy-4-amino-N-methylaniline                                                                 2-methyl-5-carbo-                                                                          1:1  acetone-water                                                                         ammonium                                                                             2:1  0                        sulfate            thoxyamino phenol       persulfate                     18   3-chloro-4-amino-N-methylaniline                                                                  2-methyl-5-N-β-                                                                       1:1  ethanol-water                                                                         ammonium                                                                             1:1  0                        dihydrochloride    hydroxyethylamino       persulfate                                             phenol                                                 19   4-nitroso-N-methylaniline                                                                         2-methyl-5-amino                                                                           1:1  ethanol-water     45                                          phenol                                                 20   monohydrate of 3-chloro-4-amino-N-                                                                2,6-dimethyl-5-ace-                                                                        1:1  acetone-water                                                                         ammonium                                                                             2:1  5                        methylaniline dihydrochloride                                                                     tylamino phenol         persulfate                     21   3-methoxy-4-amino-N-methylaniline                                                                 2,6-dimethyl-5-ace-                                                                           1:0.85                                                                           acetone-water                                                                         ammonium                                                                             2:1  0                        dihydrochloride    tylamino phenol         persulfate                     22   monohydrate of 3-chloro-4-amino-N-                                                                2-methyl 5-acetylamino                                                                       1:0.65                                                                            acetone-water                                                                         ammonium                                                                             2:1  5                        methylaniline dihydrochloride                                                                     phenol                  persulfate                     23   N-methyl paraphenylene-diamine                                                                    2,6-dimethyl phenol                                                                        1:1  acetone-water                                                                         ammonium                                                                             2:1  15                       dihydrochloride                            persulfate                     24   2-methyl-4-amino-N-methyl-aniline                                                                 2,6-dimethyl phenol                                                                        1:1  acetone-water                                                                         ammonium                                                                             2:1  15                       sulfate                                    persulfate                     25   2-chloro-4-amino-N-methyl-aniline                                                                 2,6-dimethyl phenol                                                                        1:1  acetone-water                                                                         ammonium                                                                             2:1  10                       sulfate                                    persulfate                     26   2-methyl-4-amino-N-methyl-aniline                                                                 2-methyl-5-amino                                                                           1:1  acetone-water                                                                         ammonium                                                                             2:1  10                       sulfate            phenol                  persulfate                     27   2-methoxy-4-amino N-(β-hydroxyethyl)                                                         2-methyl-5-amino                                                                           1:1  isopropanol-                                                                          ammonium                                                                             1:1  5                        aniline sulfate    phenol           water  persulfate                     28   2-methyl-4-amino-N-methyl-aniline                                                                 2,6-dimethyl-5-amino                                                                       1:1  acetone-water                                                                         ammonium                                                                             1:1  5                        sulfate            phenol hydrochloride    persulfate                     29   N-methyl paraphenylenediamine                                                                     2,6-dimethyl 3-amino                                                                       1:1  acetone-water                                                                         ammonium                                                                             1:1  0                        dihydrochloride    phenol hydrochloride    persulfate                     30   2-chloro-4-amino-N-methyl-aniline                                                                 3-acetylamino phenol                                                                       1:1  acetone-water                                                                         ammonium                                                                             2:1  5                        sulfate                                    persulfate                     31   4-amino-N-methyl-aniline dihydro-                                                                 2-methyl-5-acetylamino                                                                     1:1  acetone-water                                                                         ammonium                                                                             1 :                                                                                 0                        chloride           phenol                  persulfate                     32   2-methyl-4-amino-N-methyl-aniline                                                                 2-methyl-5-acetylamino                                                                     1:1  acetone-water                                                                         ammonium                                                                             2:1  10                       sulfate            phenol                  persulfate                     33   2-methyl-4-amino N-ethyl-aniline                                                                  2-methyl-5-acetylamino                                                                     1:1  acetone-water                                                                         ammonium                                                                             2:1  5                        sulfate            phenol                  persulfate                     34   2-chloro-4-amino-N-β-hydroxyethyl-                                                           3-acetylamino phenol                                                                       1:1  isopropanol-                                                                          ammonium                                                                             2:1  0                        aniline sulfate                     water  persulfate                     35   2-chloro-4-amino-N-β-hydroxyethyl-                                                           2-methyl-5-acetylamino                                                                     1:1  isopropanol-                                                                          ammonium                                                                             2:1  0                        aniline sulfate    phenol           water  persulfate                     36   2-chloro-4-amino N-methyl aniline                                                                 2,6-dimethyl-5-ace-                                                                        1:1  acetone-water                                                                         ammonium                                                                             2:1  5                        sulfate            tylamino phenol         persulfate                     37   2-methyl-4-amino N-methyl aniline                                                                 2,6-dimethyl-3-ace-                                                                        1:1  acetone-water                                                                         ammonium                                                                             2:1  10                       sulfate            tylamino phenol         persulfate                     38   2-chloro-4-amino N-methyl aniline                                                                 2-methyl-5-acetylamino                                                                     1:1  acetone-water                                                                         ammonium                                                                             2:1  10                       sulfate            phenol                  persulfate                     39   2-chloro-4-amino N-methyl aniline                                                                 2,6-dimethyl-3-ureido                                                                      1:1  acetone-water                                                                         ammonium                                                                             2:1  5                        sulfate            phenol                  persulfate                     40   2-chloro-4-amino-N-methyl aniline                                                                 3-ureido phenol                                                                            1:1  acetone-water                                                                         ammonium   5                        sulfate                                    persulfate                     41   2-chloro-4-amino-N-β-hydroxyethyl-                                                           2,6-dimethyl-3-ureido                                                                      1:1  acetone-water                                                                         ammonium                                                                             2:1  0                        aniline sulfate    phenol                  persulfate                     42   2-chloro-4-amino N-β-hydroxyethyl-                                                           3-ureido phenol                                                                            1:1  acetone-water                                                                         ammonium                                                                             2:1  0                        aniline sulfate                            persulfate                     43   2-chloro-4-amino-N-methylaniline                                                                  2-methyl-5-ureido                                                                          1:1  propanol-water                                                                        ammonium                                                                             2:1  0                        sulfate            phenol                  persulfate                     44   2-chloro-4-amino N-β-hydroxyethyl-                                                           2-methyl-5-ureido                                                                          1:1  isopropanol-                                                                          ammonium                                                                             2:1  0 to 5                   aniline sulfate    phenol           water  persulfate                     45   2-chloro-4-amino-N-methylaniline                                                                  2-methyl-5-carbamyl-                                                                       1:1  acetone-water                                                                         ammonium                                                                             2:1  0                        sulfate            methylamino phenol      persulfate                     46   4-amino N-methylaniline dihydro-                                                                  2-methyl-5-carbamyl-                                                                       1:1  acetone-water                                                                         ammonium                                                                             2:1  0                        chloride           methylamino phenol      persulfate                     47   4-amino-2-chloro N-methylaniline                                                                  2,5-dimethyl phenol                                                                        1:1  acetone-water                                                                         ammonium                                                                             2:1  0 to 5                   sulfate                                    persulfate                     48   monohydrate of 3-chloro 4-amino                                                                   2-chloro-5-acetylamino                                                                     1:1  acetone-water                                                                         ammonium                                                                             2:1   10                      N-methylaniline dihydrochloride                                                                   phenol                  persulfate                     __________________________________________________________________________

The present invention is illustrated by the following non-limiting examples.

Diphenylamines prepared in accordance with the present invention are listed in Table I in which Column I indicates the number of the compound prepared, which corresponds to the number of the benzoquinoneimine of Tables A and B; Column II gives the chemical name of the diphenylamine; Column III, the melting point of said diphenylamine; Column IV, the empirical formula of said diphenylamine and Column V, the elemental analysis of the diphenylamine with percentages of carbon, hydrogen and nitrogen and optionally chlorine and sulfur. For the indicated percentages, the first number indicated represents the value calculated for the empirical formula given whereas the second and third numbers represents the value found by analysis.

In Table II are listed the operating conditions for the preparation of representative ones of the compounds appearing in Table I. In Table II, Column I indicates the number of the compound prepared; Column II identifies the benzoquinoneimine initial reactant and the quantity employed to produce the diphenylamine; Column III gives the quantity of sodium hydrosulfite employed; Column IV lists the quantity of sodium hydroxide used; Column V indicates the reaction temperature and Column VI gives the quantity of ethanol added (a) to the sodium hydrosulfite solution or (b) to act as a solubilizer for the benzoquinoneimine.

The examples of use involving the dye compositions of the present invention are tabulated in Table III and the examples of use involving hair setting lotion compositions containing a cosmetic film-forming agent are tabulated in Table IV.

In Table III, Column I indicates the number of the example; Column II identifies the diphenylamine dye by the corresponding example number of the same as it appears in Table I and the percentage thereof in the composition; Column III identifies the adjuvants employed and the weight percent thereof; Column IV gives the nature and weight percent of solvent; Column V lists the nature, quantity and concentration of the oxidizing agent present in the composition; Column VI gives the pH of the composition and Columns VII and VIII indicate, respectively, the nature of the hair to be dyed and the color achieved on dyeing the same.

In Table IV, Column I indicates the number of the Example; Column II identifies the diphenylamine employed by the corresponding example number of the same as it appears in Table I and the percentage thereof in the composition; Column III identifies the chemical name, the molecular weight and the concentration or percentage of the cosmetic film-forming resin used in the composition; Column IV identifies the alcohol and amount thereof employed in the composition; Column V indicates the pH of the composition and Columns VI and VII identify respectively the nature of the hair treated with the composition and the color achieved with the said composition.

                                      TABLE I                                      __________________________________________________________________________     I                        III             V                                     Ex                                                                                 II                   M.P.                                                                              IV           ANALYSIS                              No                                                                               DIPHENYLAMINE          (°C.)                                                                      EMPIRICAL FORMULA                                                                           C %                                                                               H %                                                                               N %                                                                               Cl %                                                                               S                        __________________________________________________________________________                                                           %                        1 3,3'-dimethyl-4-hydroxy-6-acetylamino-4'-β                                                       184                                                                               C.sub.18 H.sub.23 N.sub.3 O.sub.3                                                           65.63                                                                             7.04                                                                              12.76                             (hydroxyethyl) amino                   65.47                                                                             7.12                                                                              12.64                                                                    65.39                                                                             7.25                                                                              12.59                           2 3,5-dimethyl-2-amino-4-hydroxy-3'-methoxy-                                                            162                                                                               C.sub.19 H.sub.26 N.sub.4 O.sub.3                                                           63.66                                                                             7.31                                                                              15.63                             4'-acetylaminoethylamino               63.81                                                                             7.58                                                                              15.75                           3 3-methyl-4-hydroxy-6-acetylamino-3'-chloro-4'-                                                        98 C.sub.18 H.sub.23 N.sub.4 O.sub.4 Cl                                                        50.64                                                                             5.43                                                                              13.12  7.51                       mesylaminoethylamino                   50.38                                                                             5.57                                                                              13.22  7.56                                                              50.42                                                                             5.60                                                                              13.26  7.46                     4 2-ureido-4-hydroxy-2'-methyl-4'-N-ethylamino                                                          140                                                                               C.sub.16 H.sub.20 N.sub.4 O.sub.2                                                           63.98                                                                             6.71                                                                              18.65                                                                    63.56                                                                             6.84                                                                              18.54                                                                    63.50                                                                             6.87                                                                              18.46                           5 3,3',5-trimethyl-2-acetylamino-4-hydroxy-4'-                                                          120                                                                               C.sub.20 H.sub.28 N.sub.4 O.sub.4 S                                                         57.13                                                                             6.71                                                                              13.33  7.61                       N-mesylaminoethylamino                 56.84                                                                             6.75                                                                              13.32  7.83                                                              56.98                                                                             6.57                                                                              13.47  7.81                     6 3,3'5-trimethyl-2-amino-4-hydroxy-4'-N-                                                               136                                                                               C.sub.17 H.sub.23 N.sub.3 O                                                                 71.54                                                                             8.12                                                                              14.73                             ethylamino                             71.78                                                                             8.06                                                                              14.55                                                       MW = 285 (a) 71.60                                                                             8.12                                                                              14.75                                                       MW = 289 (b)                                       7 3-methyl-4-hydroxy-6-carbamyl-methylamino-                                                            195                                                                               C.sub.17 H.sub.22 N.sub.4 O.sub.2                                                           64.94                                                                             7.05                                                                              17.82                             4'N-ethylamino            MW = 314 (a) 64.68                                                                             7.05                                                                              17.63                                                       MW = 316 (b) 64.77                                                                             7.12                                                                              17.60                           8 3-methyl-4-hydroxy-6-acetylamino-4'-N-                                                                194                                                                               C.sub.17 H.sub.21 N.sub.3 O.sub.2                                                           68.20                                                                             7.07                                                                              14.04                             ethylamino                MW = 299 (a) 68.04                                                                             7.11                                                                              14.12                                                       MW = 292 (b) 67.96                                                                             7.16                                                                              14.08                           9 3,5-dimethyl-4-hydroxy-2-acetylamino                                                                  170                                                                               C.sub.17 H.sub.21 N.sub.3 O.sub.2                                                           68.20                                                                             7.07                                                                              14.04                             4'-N-methylamino                       68.00                                                                             7.09                                                                              14.04                                                                    67.98                                                                             7.13                                                                              14.08                           10                                                                               3,5-dimethyl-4-hydroxy-3'-methoxy-4'-N-                                                               133                                                                               C.sub.16 H.sub.20 N.sub.2 O.sub.2                                                           70.56                                                                             7.40                                                                              10.29                             methylamino               MW = 270 (a) 70.32                                                                             7.20                                                                              10.26                                                       MW = 273 (b) 70.28                                                                             7.26                                                                              10.45                           11                                                                               monohydrate of 3-chloro-4-hydroxy-5-acetyla-                                                          125                                                                               C.sub. 16 H.sub.17 N.sub.3 O.sub.2 Cl.sub.2 .                                  H.sub.2 O    49.50                                                                             4.93                                                                              10.81                                                                             18.30                          mino-3'-chloro-4'-N (β-hydroxyethyl) amino                                                                       49.73                                                                             4.96                                                                              10.81                                                                             18.10                                                                 49.82                                                                             4.76                                                                              10.91                                                                             18.22                        12                                                                               3-methyl-4-hydroxy-6-acetylamino-3'-chloro-4'-                                                        206                                                                               C.sub.17 H.sub.20 N.sub.3 O.sub.2 Cl                                                        61.17                                                                             6.04                                                                              12.58                                                                             10.62                          N-ethylamino              MW = 333.5 (a)                                                                              60.67                                                                             6.16                                                                              12.27                                                                             10.48                                                    MW = 329  (b)                                                                               60.76                                                                             6.18  10.42                        13                                                                               monohydrate of 3,5-dimethyl-4-hydroxy-6-                                                              129                                                                               C.sub.19 H.sub.25 N.sub.3 O.sub.4 . H.sub.2                                                 60.46                                                                             7.21                                                                              11.13                             acetylamino-3'-methoxy-4'-N-(β-hydroxyethyl)                                                        MW = 377 (a) 60.18                                                                             7.06                                                                              10.98                             amino                     MW = 376 (b) 60.33                                                                             7.12                                                                              10.90                           14                                                                               2-acetylamino-4-hydroxy-3' -chloro-4'-N-                                                              170                                                                               C.sub.18 H.sub.22 N.sub.3 O.sub.2 Cl                                                        62.16                                                                             6.38                                                                              12.08                                                                             10.19                          butylamino                MW = 348 (a) 61.82                                                                             6.51                                                                              12.04                                                                             10.28                                                    MW = 345 (b) 61.78                                                                             6.47                                                                              11.98                                                                             10.23                        15                                                                               2-methoxy-4-hydroxy-3'-chloro-4'-acetyl-                                                              160                                                                               C.sub.17 H.sub.20 N.sub.3 O.sub.3 Cl                                                        58.36                                                                             5.72                                                                              12.01                                                                             10.15                          aminoethylamino                        58.29                                                                             5.73                                                                              12.00                                                                             10.24                                                                 58.47                                                                             5.68                                                                              11.82                                                                             10.24                        16                                                                               3-methoxy-4-hydroxy-6-acetylamino-3'-methyl-                                                          163                                                                               C.sub.18 H.sub.23 N.sub.3 O.sub.3                                                           65.65                                                                             6.99                                                                              12.77                             4'-N-ethylamino                        65.45                                                                             6.80                                                                              12.65                           17                                                                               monohydrate of 3-methyl-4-hydroxy-6-carbethoxy                                                        122                                                                               C.sub.18 H.sub.23 N.sub.3 O.sub.4 . H.sub.2                                                 59.50                                                                             6.88                                                                              11.57                             amino-3'-methoxy-4'-N-methylamino      59.30                                                                             6.81                                                                              11.82                           18                                                                               3-methyl-4-hydroxy-6-β-hydroxy-ethylamino-                                                       152                                                                               C.sub.16 H.sub.20 N.sub.3 O.sub.2 Cl                                                        59.72                                                                             6.22                                                                              13.06                             2'-chloro-4'-N-methylamino             59.62                                                                             6.38                                                                              13.07                           19                                                                               3-methyl-4-hydroxy-6-amino-4'-N-methylamino                                                           182                                                                               C.sub.14 H.sub.17 N.sub.3 O                                                                 69.11                                                                             7.04                                                                              17.27                                                                    69.16                                                                             6.95                                                                              17.36                           20                                                                               3,5-dimethyl-4-hydroxy-2-acetylamino-2'-chloro-                                                       193                                                                               C.sub.17 H.sub.20 N.sub.3 O.sub.2 Cl                                                              12.59                                                                             10.64                          4'-N-methylamino                          12.77                                                                             10.70                           21                                                                               3,5-dimethyl-4-hydroxy-2-acetylamino-2'-                                                              210                                                                               C.sub.18 H.sub.23 N.sub.3 O.sub.3                                                           65.63                                                                             7.04                                                                              12.76                             methoxy-4'-N-methylamino               65.50                                                                             6.97                                                                              12.79                           22                                                                               3-methyl-4-hydroxy-6-acetylamino-2'-chloro-                                                           210                                                                               C.sub.16 H.sub.18 N.sub.3 O.sub.2 Cl                                                        60.09                                                                             5.63                                                                              13.14                                                                             11.11                          4'-N-methylamino                       60.05                                                                             5.90                                                                              12.95                                                                             10.94                        23                                                                               3,5-dimethyl-4-hydroxy-4'-N-methylamino                                                               120                                                                               C.sub.15 H.sub.18 N.sub.2 O                                                                 74.35                                                                             7.49                                                                              11.56                                                                    74.45                                                                             7.38                                                                              11.74                           24                                                                               dihydrochloride of 3,3',5-trimethyl-4-                                                                200                                                                               C.sub.16 H.sub.20 N.sub.2 O .                                                                     8.51                                                                              21.53                          hydroxy-4'-N-methylamino                                                                              (c)                   8.74                                                                              21.31                        25                                                                               3,5-dimethyl-4-hydroxy-3'-chloro-4'-N-                                                                75 C.sub.15 H.sub.17 N.sub.2 O                                                                 65.09                                                                             6.14                                                                              10.12                                                                             12.84                          methylamino                            65.36                                                                             6.34                                                                              10.28                                                                             13.09                        26                                                                               3,3'-dimethyl-4-hydroxy-6-amino-4'-N-                                                                 192                                                                               C.sub.15 H.sub.19 N.sub.3 O                                                                 70.00                                                                             7.44                                                                              16.33                             methylamino                            69.80                                                                             7.33                                                                              16.21                           27                                                                               monohydrate of 3-methyl-4-hydroxy-6-amino-4'-                                                         110                                                                               C.sub.16 H.sub.21 N.sub. 3 O.sub.3 . H.sub.2                                   O            59.81                                                                             7.10                                                                              13.08                             N-(β-hydroxyethyl)amino-3'-methoxy                                                                               59.87                                                                             6.70                                                                              13.07                           28                                                                               semi-hydrate of 3,3',5-trimethyl-4-hydroxy-2-                                                         145                                                                               C.sub.16 H.sub.21 N.sub.3 O . 0.5 H.sub.2                                                   68.57                                                                             8.21                                                                              15.00                             amino-4'-N-methylamino                 68.53                                                                             7.84                                                                              14.95                           29                                                                               3,5-dimethyl-4-hydroxy-2-amino-4'40 -N-methyl-                                                        135                                                                               C.sub.15 H.sub.19 N.sub.3 O                                                                 70.00                                                                             7.44                                                                              16.33                             amino                                  69.70                                                                             7.26                                                                              16.57                           30                                                                               2-acetylamino-4-hydroxy-3'-chloro-4'-N-                                                               182                                                                               C.sub.15 H.sub.16 N.sub.3 O.sub.2 Cl                                                        58.92                                                                             5.24                                                                              13.74                                                                             11.62                          methylamino                            58.99                                                                             5.37                                                                              13.88                                                                             11.48                        31                                                                               3-methyl-4-hydroxy-6-acetylamino-4'-N-methyl-                                                         178                                                                               C.sub.16 H.sub.19 N.sub. 3 O.sub.2                                                          67.34                                                                             6.71                                                                              14.73                             amino                                  67.37                                                                             6.90                                                                              14.70                           32                                                                               3,3'-dimethyl-4-hydroxy-6-acetylamino-4'-N-                                                           201                                                                               C.sub.17 H.sub.21 N.sub.3 O.sub.2                                                           68.20                                                                             7.07                                                                              14.04                             methylamino                            68.40                                                                             6.99                                                                              14.06                           33                                                                               3,3'-dimethyl-4-hydroxy-6-acetylamino-4'-N-                                                           205                                                                               C.sub.18 H.sub.23 N.sub.3 O.sub.2                                                           69.01                                                                             7.35                                                                              13.42                             ethylamino                             69.26                                                                             7.00                                                                              13.58                           34                                                                               2-acetylamino-4-hydroxy-3'-chloro-4'-N                                                                121                                                                               C.sub.16 H.sub.18 N.sub.3 O.sub.3 Cl                                                        57.22                                                                             5.36                                                                              12.51                             (β-hydroxyethyl) amino            57.26                                                                             5.26                                                                              12.40                           35                                                                               3-methyl-4-hydroxy-6-acetylamino-3'-chloro-                                                           175                                                                               C.sub.17 H.sub.20 N.sub.3 O.sub.3 Cl                                                        58.37                                                                             5.72                                                                              12.02                             4'-N-(β-hydroxyethyl)amino        58.24                                                                             5.96                                                                              12.04                           36                                                                               3,5-dimethyl-4-hydroxy-2-acetylamino-                                                                 229                                                                               C.sub.17 H.sub.20 N.sub.3 O.sub.2 Cl                                                        61.17                                                                             5.99                                                                              12.59                                                                             10.64                          3'-chloro-4'-N-methylamino             61.14                                                                             6.14                                                                              12.79                                                                             10.56                        37                                                                               3,3'5-trimethyl-4-hydroxy-2-acetylamino-                                                              220                                                                               C.sub.18 H.sub.23 N.sub.3 O.sub.2                                                           68.98                                                                             7.40                                                                              13.41                             4'-N-methylamino                       68.93                                                                             7.51                                                                              13.64                           38                                                                               3-methyl-4-hydroxy-6-acetylamino-3'-chloro-                                                           203                                                                               C.sub.16 H.sub.18 N.sub.3 O.sub.2 Cl                                                        60.09                                                                             5.63                                                                              13.14                                                                             11.11                          4'-N-methylamino                       60.30                                                                             5.82                                                                              13.34                                                                             10.97                        39                                                                               3,5-dimethyl-2-ureido-4-hydroxy-3'-chloro-                                                            232                                                                               C.sub.16 H.sub.19 N.sub.4 O.sub.2 Cl                                                        57.40                                                                             5.68                                                                              16.74                                                                             10.60                          4'-N-methylamino                       57.60                                                                             5.76                                                                              16.86                                                                             10.58                        40                                                                               2-ureido-4-hydroxy-3'-chloro-4'-N-methylamino                                                         213                                                                               C.sub.14 H.sub.15 N.sub.4 O.sub.2 Cl                                                        54.81                                                                             4.89                                                                              18.27                                                                             11.58                                                                 54.42                                                                             5.05                                                                              18.54                                                                             11.59                        41                                                                               semi-hydrate of 3,5-dimethyl-4-hydroxy-2-                                                             170                                                                               C.sub.17 H.sub.21 N.sub.4 O.sub.3 Cl .                                         0.5H.sub.2 O 54.62                                                                             5.89                                                                              14.99                                                                             9.50                           ureido-3'-chloro-4'-N-(β-hydroxyethyl)amino                                                                      54.48                                                                             5.70                                                                              15.19                                                                             9.36                         42                                                                               2-ureido-4-hydroxy-3'-chloro-4'-N-(β-hydroxy-                                                    183                                                                               C.sub.15 H.sub.17 N.sub.4 O.sub.3 Cl                                                        53.49                                                                             5.05                                                                              16.64                             ethyl)amino                            53.20                                                                             5.05                                                                              16.50                           43                                                                               3-methyl-4-hydroxy-6-ureido-3'-chloro-4'-N-                                                           216                                                                               C.sub.15 H.sub.17 N.sub.4 O.sub.2 Cl                                                        56.16                                                                             5.30                                                                              17.47                                                                             11.07                          methylamino                            56.14                                                                             5.60                                                                              17.63                                                                             11.09                        44                                                                               3-methyl-4-hydroxy-6-ureido-3'-chloro-4'-N-                                                           173                                                                               C.sub.16 H.sub.19 N.sub.4 O.sub.3 Cl                                                        54.78                                                                             5.42                                                                              15.97                                                                             10.13                          (β-hydroxyethyl)amino             54.93                                                                             5.67                                                                              16.13                                                                             9.99                                                                           9.94                         45                                                                               3-methyl-4-hydroxy-6-carbamylmethylamino-                                                             218                                                                               C.sub.16 H.sub.19 N.sub.4 O.sub.2 Cl                                                        57.40                                                                             5.68                                                                              16.74                                                                             10.61                          3'-chloro-4'-N-methylamino             57.08                                                                             5.90                                                                              17.00                                                                             10.34                        46                                                                               3-methyl-4-hydroxy-6-carbamylmethylamino-                                                             197                                                                               C.sub.16 H.sub.20 N.sub.4 O.sub.2                                                           63.98                                                                             6.71                                                                              18.65                             4' -N-methylamino                      63.84                                                                             6.92                                                                              18.86                           47                                                                               3,6-dimethyl-4-hydroxy-3'-chloro-4'-N-                                                                95 C.sub.15 H.sub.17 Cl N.sub.2 O                                                              65.09                                                                             6.19                                                                              10.12                             methylamino                            64.88                                                                             6.39                                                                              10.13                           48                                                                               3,2'-dichloro-4-hydroxy-6-acetylamino-4'-                                                             190                                                                               C.sub.15 H.sub.15 N.sub.3 Cl.sub.2 O.sub.2                                                  52.96                                                                             4.44                                                                              12.35                                                                             20.84                          N-methylamino                          53.05                                                                             4.71                                                                              12.20                                                                             20.62                        49                                                                               3-methoxy-4-hydroxy-6-amino-4'-N-methylamino                                                             C.sub.16 H.sub.17 N.sub.3 O.sub.2                  __________________________________________________________________________      (a) molecular weight, calculated                                               (b) molecular weight found by potentiometric determination in acetic acid      with perchloric acid                                                           (c) with decomposition                                                   

                                      TABLE II                                     __________________________________________________________________________                                            IV      VI                                                       III           NaOH                                                                               V   Ethanol                         I   II                   quantity                                                                            Na.sub.2 S.sub.2 O.sub.4 . 2H.sub.2                                                     1N  Temp.                                                                              (ml)                            No                                                                               BENZOQUINONEIMINE      (g)  (g)      (ml)                                                                               (°C.)                                                                       (a)                                                                               (b)                          __________________________________________________________________________      1                                                                               N[(4'-β-hydroxyethylamino-3'-methyl)phenyl]                                                      3.09 8        80  30                                    2-methyl-5-acetylamino                                                        2                                                                               N-[(4'-acetylaminoethylamino-3'-methoxy)                                                              1    3        33  20  6                                 phenyl]2,6-dimethyl-3-amino                                                   3                                                                               N-[(4'-mesylaminoethylamino-3'-chloro)                                                                1    3        33  20  6                                 phenyl]2-methyl-5-acetylamino                                                 4                                                                               N-[(4'-ethylamino-2'-methyl)phenyl]3-ureido                                                           1    4        35  25     12                            5                                                                               N-[(4'-mesylaminoethylamino-3'-methyl)                                                                1    3        33  15  6                                 phenyl]2,6-dimethyl-3-acetylamino                                             6                                                                               N-[(4'-ethylamino-3'-methyl)phenyl]2,6-di-                                                            1    6        50  40     10                             methyl-3-amino                                                                7                                                                               N-[(4'-ethylamino)phenyl]2-methyl-5-carbamyl-                                                         1    5        50  25     15                             methylamino                                                                   8                                                                               N-[(4'-ethylamino)phenyl]2-methyl-5-acetyl-                                                           1    6        50  25     15                             amino                                                                         9                                                                               N-[(4'-methylamino)phenyl]2,6-dimethyl-3-                                                             1    3        33  20     12                             acetylamino                                                                  10                                                                               N-[(4'-methylamino-3'-methoxy)phenyl]2,6-                                                             1    3        33  30  6                                 dimethyl                                                                     11                                                                               N-[(4'-β-hydroxyethylamino-3'-chloro)phenyl]                                                     1    3        33  15  6                                 3-chloro-6-acetylamino                                                       12                                                                               N-[(4'-ethylamino-3'-chloro)phenyl]2-methyl-                                                          1    3        33  25  10                                5-acetylamino                                                                13                                                                               N-[(4'-β-hydroxyethylamino-3'-methoxy)phenyl]                                                    1    3        33  20  6                                 2,6-dimethyl-5-acetylamino                                                   14                                                                               N-[(4'-butylamino-3'-chloro)phenyl]3-acetyl-                                                          1    4        80  25  10                                amino                                                                        15                                                                               N-[(4'-β-acetylaminoethylamino-3'-chloro)                                                        5.2  10       100 15     25                             phenyl]3-methoxy                                                             16                                                                               N-[(4'-ethylamino-3'-methyl)phenyl]2-methoxy-                                                         3.27 6        60  20     20                             5-acetylamino                                                                17                                                                               N-[(4'-methylamino-3'-methoxy)phenyl]2-methyl-                                                        3.43 8        80  10     35                             5-carbethoxyamino                                                            18                                                                               N-[(4'-methylamino-2'-chloro)phenyl]2-methyl-                                                         3.2  6        60  25     20                             5-β-hydroxy-ethylamino                                                  19                                                                               N-[(4'-methylamino)phenyl]2-methyl-5-amino                                                            33   80       800 25     200                          20                                                                               N-[(4'-methylamino-2'-chloro)phenyl]2,6-di-                                                           39.8 70       720 20     250                            methyl-3-acetylamino                                                         21                                                                               N-[(4'-methylamino-2'-methoxy)phenyl]2,6-di-                                                          22   40       400 15     150                            methyl-3-acetylamino                                                         48                                                                               monohydrate of N-[(4'-methylamino-2'-chloro)                                                          3    10       120 5      20                             phenyl]2-chloro-5-acetylamino                                                49                                                                               monohydrate of N-[(4'-methylamino)phenyl]2-                                                           4.12 9        90  20                                    methoxy-5-amino                                                              __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________     I   II     III        IV       V           VI VII  VIII                                                       OXIDIZING                                           DYE    ADJUVANT   SOLVENT  AGENT                                           Ex No                                                                              Ex No                                                                              %  nature  %  Nature                                                                               %  nature                                                                              ml conc                                                                               pH HAIR COLOR                       __________________________________________________________________________     A1   8   0.05                                                                             AL 10.5 OE (1)                                                                         5  butyl 5  H.sub.2 O.sub.2                                                                     100                                                                               6%  5.6                                                                               D (a)                                                                               pearly light blue                                 glycol                                                   A2  12  0.35                                                                              CMC (2) 10          H.sub.2 O.sub.2                                                                     100                                                                               6%  10 "    plearly light mauve         A3   6  0.27                                                                              (NP 4 OE (3)                                                                           5           H.sub.2 O.sub.2                                                                     25 6%  6  B95 (b)                                                                             slightly pink                          (NP 9 OE (3)                                                                           5                               ash beige                   A4   9  0.1           EMDE (4)                                                                             10 PSA  100                                                                               1%  8  D (a)                                                                               pearly light blue           A5  14  0.05          iso-  40 H.sub.2 O.sub.2                                                                     30 6%  8  "    pearly glycine                                    propanol                                                 A6   2  0.60          ethanol                                                                              20             11 "    deep violet                 A7   3  0.40                                                                              DC (5)  10          H.sub.2 O.sub.2                                                                     35 6%  10.5                                                                              "    very luminous mauve         A8   4  0.20                                                                              AL 10.5 OE (1)                                                                         20          PU   100                                                                               10% 6.1                                                                               "    very luminous                                                                  emerald green               A9   5  0.03                                                                              AL 10.5 OE (1)                                                                         5           H.sub.2 O.sub.2                                                                     25 6%  6.5                                                                               "    very silvery                                                                   light blue                  A10 11  0.07                                                                              CMC (2) 3.5                                                                               iso-  30 H.sub.2 O.sub.2                                                                     50 6%  8.6                                                                               "    pearly myosotis blue                              propanol                                                 A11 13  0.1                                                                               LSS 19 (6)                                                                             20          H.sub.2 O.sub.2                                                                     50 6%  9.2                                                                               D (a)                                                                               very pale                              EDTA (7)                                emerald green               A12  7  0.2                                                                               oleyl-  5           H.sub.2 O.sub.2                                                                     50 6%  9  "    very luminous                          (OCH.sub.2                              deep mauve                              ##STR4##                                                                      oleyl-  5                                                                      (OCH.sub.2                                                                      ##STR5##                                                           A13  1  0.41          ethanol                                                                              35 PU   100                                                                               10% 9  "    silvery light                                                                  blue gray                   A14 11  0.20                                                                              LSS 19 (6)                                                                             20          H.sub.2 O.sub.2                                                                     60 6%  9.8                                                                               B95 (b)                                                                             ash beige                       C1  0.06                                                                              EDTA (7)                                                                               0.2                                                             C2  0.05                                                                       C3  0.12                                                                       C4  0.25                                                                   A15  7  0.10                                                                              AL 10.5 OE (1)                                                                         5  butyl-                                                                               5              8  D (a)                                                                               light copper chestnut           C5  0.12          glycol                                                       C6  0.04                                                                       C7  0.05                                                                   A16  9  3  DC (5)  10          H.sub.2 O.sub.2                                                                     100                                                                               6%  12 B95 (b)                                                                             silvery lavender blue       A17 29  0.3                                                                               AL 10.5 OE (1)                                                                         5  butyl-                                                                               5              7.5                                                                               D (a)                                                                               purple violet                                     glycol                                                   A18 32  2  LSS 19 (6)                                                                             20                      10.6                                                                              "    sky blue                               EDTA (7)                                                                               0.2                                                         A19 20  0.2                                                                               AO 2 OE (8)                                                                            3.7                                                                               propylene-                                                                           7.4                                                                               H.sub.2 O.sub.2                                                                     30 6%  9.5                                                                               "    silvery light                          AO 4 OE (8)                                                                            5.5                                                                               glycol                       blue gray                   A20 34  1  AcP (9) 2.25                                                                              ethanol                                                                              25 H.sub.2 O.sub.2                                                                     60 6%  10 "    extremely rich                                                                 violet blue                 A21 37  1  AL 10.5 OE (1)                                                                         5  butyl-                                                                               5              8  "    silvery myosotis blue                             glycol                                                   A22 28  3  CMC (2) 4.25                                                                              ethanol                                                                              15 H.sub.2 O.sub.2                                                                     25 6%  10.5                                                                              B95 (b)                                                                             purple                      A23 40  1  LSS 19 (6)                                                                             20          H.sub.2 O.sub.2                                                                     40 6%  10.5                                                                              D (a)                                                                               silvery mauve gray                     EDTA (7)                                                                               0.2                                                         A24 31  3  CMC (2) 4.5                                                                               ethanol                                                                              10             5.5                                                                               B95 (b)                                                                             deep ultramarine blue       A25 23  2  DC (5)  8  ethanol                                                                              20 H.sub.2 O.sub.2                                                                     20 6%  10 D (a)                                                                               very luminous                                                                  royal blue                  A26 19  1.2                                                                               AO 2 OE (8)                                                                            3.70                                                                              propylene-                                                                           7.4                                                                               PU   lg     10.5                                                                              B95 (b)                                                                             violet                                 AO 4 OE (8)                                                                            5.50                                                                              glycol                                                   A27 39  1.5                                                                               AL 10.5 OE (1)                                                                         5                       6.5                                                                               D (a)                                                                               silvery pale mauve          A28 41  2.5                                                                               NP 4 OE (3)                                                                            16 ethanol                                                                              20             9.5                                                                               "    pearly raw silk                        NP 9 OE 16                              with mauve glints           A29 30  0.5                                                                               CMC (2) 4  ethanol                                                                              20             8  "    very luminous                                                                  violet blue                 A30 21  0.65                                                                              AL 10.5 OE (1)                                                                         20          H.sub.2 O.sub.2                                                                     25 6%  8  "    turquoise blue              A31 38  0.65          ethanol                                                                              20 H.sub.2 O.sub.2                                                                     25     8.5                                                                               "    silvery very                                      EMDE (4)                                                                             8                      light mauve                 A32 33  3  DC (5)  8  ethanol                                                                              0              11 "    silvery very light                                                             turquoise blue              A33 46  1.5                                                                               DC (5)  7.5                                                                               ethanol                                                                              25 H.sub.2 O.sub.2                                                                     50 6%  9  B95 (b)                                                                             violet beige gray           A34 43  0.55                                                                              AO 20E (8)                                                                             3.7                                                                               propylene-                                                                           7.4                                                                               H.sub.2 O.sub.2                                                                     50 6%  9  D (a)                                                                               purple                                 AO 40E (8)                                                                             7.5                                                                               glycol                                                   A35 24  1.5                                                                               LSA (10)                                                                               5                       8  "    azure blue                  A36 22  3  LSS 19 (6)                                                                             20          PU   lg     10 "    silvery light gray                     EDTA (7)                                                                               0.2                                                         A37 44  1             ethanol                                                                              10 H.sub.2 O.sub.2                                                                     20 6%  9.5                                                                               D (a)                                                                               perme                                             EMDE (4)                                                                             8                                                  A38  7  0.75                                                                              NP 40E (3)                                                                             15 ethanol                                                                              25 H.sub.2 O.sub.2                                                                     25 6%  9  "    mauve                                  NP 90E (3)                                                                             15                                                          A39 42  2  AcP (9) 3.6                                                                               ethanol                                                                              20 H.sub.2 O.sub.2                                                                     60 6%  10.5                                                                              B95 (b)                                                                             violet gray                 A40 48  0.4                                                                               AcP (9) 2.5                                                                               ethanol                                                                              25 H.sub.2 O.sub.2                                                                     60 6%  10 D (a)                                                                               very luminous glycine       A41 49  0.75                                                                              AL 10.5 OE (1)                                                                         20          H.sub.2 O.sub.2                                                                     50 6%  10.5                                                                              B95 (b)                                                                             mauve                       __________________________________________________________________________                                                        gray                         (a) D = bleached hair                                                          (b) B95 = 95% naturally white hair                                             (1) AL 10.50E = laurylalcohol oxyethylenated with 10.5 moles of ethylene       oxide                                                                          (2) CMC = carboxymethyl cellulose                                              (3) NP × OE = nonylphenol polyoxyethylenated with x moles of             ethylene oxide                                                                 (4) EMDE = monomethyl ester of diethylene glycol                               (5) DC = diethanolamides of the fatty acids of coprah                          PSA = ammonium persulfate                                                      PU = urea peroxide                                                             (6) LSS 19 = mixture constituted by 19% lauryl alcohol oxyethylenated wit      2 moles of ethylene oxide and 81% of the sodium sulfate salt of this same      oxyethylenated alcohol.                                                        (7) EDTA = ethylenediamine tetracetic acid                                     C.sub.1 = dihydrochloride of methoxyparaphenylene diamine                      C.sub.4 = paraaminophenol                                                      C.sub.2 = 6hydroxyphenomorpholine                                              C.sub.3 =2,4diaminoanisole dihydrochloride                                     C.sub.5 = 3methoxy-4,6-diamino-4'-hydroxy-diphenylamine dihydrochloride        C.sub.6 = 2,6diamino-4-N,N-diethylaminophenol,trihydrochloride                 C.sub.7 = nitrometaphenylenediamine                                            (8) AO × OE = oleyl alcohol oxyethylenated with x moles of ethylene      oxide                                                                          (9) AcP = polyacrylic acid (MW = 2 to 3 million)                               (10) L.S.A. = lauryl ammonium sulfate                                    

                                      TABLE IV                                     __________________________________________________________________________     I  II      III                  IV       V  VI  VII                            Ex.                                                                               DYE     POLYMER              ALCOHOL                                        No Ex No                                                                              wt %                                                                               Name    M.W.   Cps % Name   % pH HAIR                                                                               Color                          __________________________________________________________________________     B1  2  0.50                                                                               VP 30/VA 70                                                                            160,000      ethanol                                                                               50                                                                               10.5                                                                              B95 (b)                                                                            violet light chestnut             12  0.40                                                                       C8  0.10                                                                       C9  0.20                                                                    B2 12  0.53                                                                               PVP      40,000    2 isopropanol                                                                           25                                                                               9.7                                                                               D (a)                                                                              deep violet                    B3 10  0.05                                                                               VP 30/VA70                                                                             160,000    2 ethanol                                                                               40                                                                               9.5                                                                               D (a)                                                                              very luminous pearly                                                           blue                           B4 10  0.07                                                                               VA 90/CA10                                                                              45,000-   1 ethanol                                                                               40                                                                               10 B95 (b)                                                                            pink beige                        4   0.22         50,000                                                        C10 0.22                                                                       C9  0.09                                                                    B5 15  0.15                                                                               VA90/CA10                                                                               45,000-   2 ethanol                                                                               50                                                                               10 D (a)                                                                              pearly mauve                                       50,000                                                     B6 16  0.60                                                                               PVP      40,000    2 isopropanol                                                                           25                                                                               7  "   very luminous periwinkle                                                       blue                           B7 17  0.45                                                                               Gafquat 734                                                                            100,000    2 isopropanol                                                                           20                                                                               7  "   light turquoise blue           B8 25  0.25                                                                               VA90/CA10                                                                               45,000-   1 ethanol                                                                               36                                                                               6.5                                                                               "   silvery glycine                                    50,000                                                     B9 26  0.40                                                                               VP60/VA40      *3.3 to                                                                            2 isopropanol                                                                           35                                                                               4.5                                                                               B95 (b)                                                                            dark violet                                              4                                                    B10                                                                               27  0.40                                                                               VP60/VA40      3.3 to                                                                             2 isopropanol                                                                           35                                                                               8  D (a)                                                                              violet                                                   4                                                    B11                                                                               35  0.30                                                                               PVP      40,000    2 isopropanol                                                                           25                                                                               8  "   very luminous light                                                            mauve                          B12                                                                               45  0.30                                                                               VA80.5/AS15/   4.5 2.5                                                                              ethanol                                                                               50                                                                               7.5                                                                               D (a)                                                                              salmon                                    AOA4.5                                                              B13                                                                               36  0.25                                                                               VP 30/VA70                                                                             160,000    2 ethanol                                                                               40                                                                               4  "   silvery light mauve gray       B14                                                                               18  0.40                                                                               Gantrez ES435  0.962                                                                              1 ethanol                                                                               45                                                                               9  "   pearly parme                   B15                                                                               47  0.3 VP60/VA40      3.5 2 isopropanol                                                                           35                                                                               7  D (a)                                                                              pearly light raw silk                                                          with                                                                           mauve glints                   __________________________________________________________________________      In Table IV, above:                                                            *viscosity determined starting with a 5% solution in ethanol at a              temperature of 25° C.                                                   C8 = N[4'-hydroxy)phenyl]-2,6-dimethyl benzoquinoneimine;                      C9 = nitroparaphenylene diamine                                                C10 = 1γ-amino propylamino anthraquinone                                 VP30/VA70 = copolymer of 30% vinylpyrrolidone and 70% vinyl acetate sold       under the mark PVP/VA E335;                                                    VP60/VA40 =  copolymer of 60% vinylpyrrolidone and 40% vinyl acetate sold      under the mark PVP/VA S 630;                                                   VA90/CA10 = copolymer of 90% vinyl acetate and 10% crotonic acid;              Gafquat 734 = quaternary copolymer of polyvinylpyrrolidone;                    VA80.5/AS15/AOAA4.5 = copolymer of 80.5% vinyl acetate, 15% allyl stearat      and 4.5% allyloxyacetic acid; and                                              Gantrez ES 435 = monobutyl ester of the copolymer of maleic anhydride and      methyl vinyl ether.                                                       

What is claimed is:
 1. Diphenylamine of the formula: ##STR6## wherein R₁ and R₄ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 1-6 carbon atoms, lower alkoxy having 1-6 carbon atoms, amino, N-lower alkyl amino wherein the alkyl moiety has 1-6 carbon atoms, N-lower hydroxy alkyl amino wherein the alkyl moiety has 1-6 carbon atoms and acylamino wherein the acyl moiety has 2-7 carbon atoms, with at least one of R₁ and R₄ being said acylamino;R₂ and R₃ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 1-6 carbon atoms, lower alkoxy having 1-6 carbon atoms and acylamino wherein the acyl moiety has 2-7 carbon atoms; R₅ and R₆ each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 1-6 carbon atoms and lower alkoxy having 1-6 carbon atoms with the proviso that when both R₅ and R₆ are other than hydrogen at least one of R₅ and R₆ occupies a position meta to --NHR₇ ; and R₇ represents a member selected from the group consisting of hydroxy alkyl having 1-6 carbon atoms, amino alkyl having 1-6 carbon atoms, mono alkyl amino alkyl wherein each alkyl moiety has 1-6 carbon atoms and dialkyl amino alkyl wherein each alkyl moiety has 1-6 carbon atoms.
 2. The diphenylamine of claim 1 in the form of a salt selected from the group consisting of hydrochloride, hydrobromide, sulfate and phosphate.
 3. The diphenylamine of claim 1 which is 3,5-dimethyl-4-hydroxy-6-acetylamino-3'-methoxy-4'-N-(β-hydroxy ethyl) amino. 